1-halo-2-aryloxy-vinyl (2)-phosphates

ABSTRACT

1-HALO-2-ARYLOXY-VINYL(2)-PHOSPHATES ARE VERY EFFECTIVE COMPOUNDS FOR COMBATING PESTS, SUCH AS INSECTS, NEMATRODES AND REPRESENTATIVES OF THE ORDER ACARINA AS WELL AS PLANT-PATHOGENIC BACTERIA AND FUNGI. THE NEW PHOSPHATES MAY BE USED IN THE FORM OF PESTICIDAL PREPARATIONS.

United States Patent US. Cl. 260-951 18 Claims ABSTRACT OF THE DISCLOSURE 1-halo-2-aryloxy-vinyl(2)phosphates are very eifective compounds for combating pests, such as insects, nema todes and representatives of the order Acarina as well as plant-pathogenic bacteria and fungi. The new phosphates may be used in the form of pesticidal preparations.

This invention relates to phosphoric acid esters having pesticidal properties, and to a process for their preparation.

The present invention provides compounds having the formula in which Hal represents a bromine atom or a chlorine atom, R and R which may be the same or diiferent, each represents an alkyl radical having from 1 to 4 carbon atoms and R represents an aryl radical, especially a phenyl or naphthyl radical, which may be substituted by a halogen atom, an alkyl radical having from 1 to 4 carbon atoms, an alkoxy radical having from 1 to 4 carbon atoms, an alkylthio radical having from 1 to 4 carbon atoms, an alkylsulphinyl or alkylsulphonyl radical having from 1 to 4 carbon atoms, -NO CF CN, SCN, a COOalkyl radical, the alkyl moiety of which has from 1 to 4 carbon atoms or a COalkyl radical, the alkyl moiety of which has from 1 to 4 carbon atoms. The term halogen as used herein encompasses fluorine, chlorine, bromine and iodine.

Preferred compounds are those having the Formula I, in which Hal represents a chlorine atom or a bromine atom, R and R each represent a methyl or ethyl radical and R represents a phenyl group which may be substituted by one or more of the following substituents:

halogen, methyl, ethyl, methoxy, ethoxy, methylmercapto, methylsulphinyl, methylsulphonyl, N0 CFg,

CN, --SCN, carbethoxy, carbomethoxy, acetyl or propionyl.

The compounds which are especially preferred are those in which Hal represents a chlorine atom and R represents a phenyl group substituted by one or more of the following substituents:

chlorine, bromide, iodine, CN, NO or CF;,, and which can additionally also contain a methyl or ethyl group.

The phosphoric acid esters of the Formula I are, for example, active against insects, nematodes and representatives of the order Acarina, and also against plantpathogenic bacteria and fungi. When used in apropriately greater amounts, they also show herbicidal and defoliating action.

Their main field of use is combatting all stages of development of sucking and biting insects and Acarina, that is to say, of eggs, larvae, pupae, chrysales and adults or imagines.

The sucking insects include Diptera and Hymenoptera,

3,732,343 Patented May 8, 1973 for example, aphids (Aphidae) such as Myzus persicae, Doralis fabae, Rhopalosiphum padi, Macrosiphum pisi, Macrosiphum solarzijolii, Cryptomyzus korschelti, Sappaphis mali, Hyalopterus arundinis and Myzus cerasi, shield lice and woolly lice (Coccina), for example, Aspidiozus hederae, Lecanium hesperidum Pseudococcus maritimus, and varieties of Thrips (Thysanoptera), for example, Hercinothrips femoralis, bugs, for example, Piesma quadrata, Rhondnius prolixus and Triatoma infestans, and cicadas, for example, Euscelis bilobatus Or Nephotettix bipunctatus.

Amongst the biting insects, there should be mentioned Lepidoptera and Coleoptera, for example, Plutella maculipennis, Lymantrz'a dispar, Euproctis chrysorrhoea, Malocosoma neustria, Mamestra brassicae, Agrotis segetum, Pieris brassicae and Pradenia litum, Ephestia kuhniella, and Galleria mellonella, as well as storage pests, for example, Dermestes frischii, T rogoderma granarius, Tribolium castaneum, Calandra and Sitophilus zea mais, Stegobium paniceum, T enebrio molitor, Oryzaephilus surinamensis, Blattela germanica, Periplaneta americana, Blatta orientalis, Blaberus gigantus, Blaberus fuscus, Gryllus dom'esticus, S itophilus granarius and Leptinotarsa decemlineata; varieties which inhibit the soil, for exam ple, Agriotes sp. and Melolontha melontha; and termites, for example, Leucotermes sp. or Leucotermes flavipes.

A substantial number of pests is to be found under the order Acarina, for example, mites and amongst these especially spider mites (Tetranychidae) for example Tetranychus telarius, T. althaeae, T. urticae, Paratetranychus pilosus and Panonychus ulmi, and gall mites (Eriophyes ribis) and Tarsonemidae, for example, Hemitarsomenus latus or Tassonemus pallidus.

The order Acarina however also includes the ticks, that is to say, ectoparasites such as Boophilus microplus, Dermanyssus gallinae, Ornithonyssus bacoti, Ornithonyssus sylvarum, Rhipicephalus bursa, Penumonyssus caninum, Laelaps nutalli, Acarapis woodi and Psorergates ovis.

This summary of pests does not in any way claim to be complete. Fundamentally, the phosphates of the Formula I have a powerful action against insects and Acarina which are known as pests in crop plant cultures. Thus, say, the rice stem borer Chilo suppressalis is completely destroyed by 0.02% of the compounds of the present invention.

Apart from the insecticidal and acaricidal action, the compounds of the Formula I also show a powerful action against plant-pathogenic nematodes, of which the following orders may be mentioned:

Aphelenchoides, for example, Aphelenchust ritzemabosi, Aphelenchus fragariae, and Aphelenchus oryzae, Ditylenchoides, for example Ditylenchus dipsaci, Meloidogyne, for example Meloidogyne arenaria and Meloidogyne incognita, and cyst-forming nematodes (Heterodera), for example, Heterodera rostochienis, and Heterodera schachtii, and root nematodes such as Pratylenchus, Paratylenchus, Rotylenchus, Xiphinema and Rahadopholus.

The present invention also provides pesticidal preparations which comprise, as active ingredient, at least one phosphoric acid ester of the formula inwhich Hal, R R and R have the meanings specified above, together with a suitable carrier, for example, a solvent, diluent, dispersing agent, emulsifier, adhesive, thickener, or binder and, if desired other pesticides, for example, insecticides, acaricides, nematocides, bactericides and fungicides.

The active ingredients can be used in the most diverse manner, for example, in the form of sprays, concentrates, dusting powders, scattering agents, granules, fly plates or impregnated strips.

In order to manufacture directly sprayable solutions of the compounds of the Formula I it is for example possible to use mineral oil fractions of high to medium boiling range, such as diesel oil or kerosene, coal tar oil and oil of vegetable or animal origin, as well as hydrocarbons, for example alkylated naphthalenes or tetrahydronaphthalene, optionally using xylene mixtures, cyclohexanols, ketones and also chlorinated hydrocarbons, such as trichlorethane, trichlorethylene or trichlorobenzenes and tetrachlorobenzenes. Advantageously, organic solvents of boiling point above 100 C. are used.

Aqueous application forms are particularly appropriately prepared from emulsion concentrates, pastes or Wettable spraying powders by adding water. Possible emulsifiers or dispersing agents are non-ionic products, for example condensation products of aliphatic alcohols, amines or carboxylic acids, having a long-chain hydrocarbon radical of about to carbon atoms, with ethylene oxide, for example the condensation product of octadecyl alcohol and to mols of ethylene oxide, or that of technical oleylamine and 15 mols of ethylene oxide or that of dodecylmercaptan and 12 mols of ethylene oxide. As anionic emulsifiers there may be mentioned: the sodium salt of dodecyl alcohol sulphuric acid ester, the sodium salt of dodecyl benzenesulphonic acid, the potassium or triethanolamine salt of oleic acid or of abietic acid or of mixtures of these acids, or the sodium salt of a petroleumsulphonic acid. Possible cationic dispersing agents are quaternary ammonium compounds, such as cetylpyridinium bromide, or dihydroxyethylbenzyldodecylammonium chloride.

Talc, kaolin, bentonite, calcium carbonate and calcium phosphate, but also charcoal, cork powder, wood flour and other materials of vegetable origin, can be employed for the manufacture of dusting agents and sprinkling agents.

Granules can be manufactured very simply by dissolving an active substance of Formula I in an organic solvent and applying the solution thus obtained to a granular mineral, for example attapulgite, SiO granicalcium, bentonite and the like, and then again evaporating the organic solvent.

Polymer granules can also be used. They can be manufactured by mixing the active substances of Formula I with polymerisable compounds(urea/formaldehyde, dicyandiamde/formaldehyde, melamine/formaldehyde or others), after which a polymerisation is carried out under mild conditions, which leaves the active substances unaffected, With the granulation being carried out whilst the gel formation is still proceeding. It is more advantageous to impregnate finished porous polymer granules (urea/ formaldehyde, polyacrylonitrile, polyesters or others) having a particular surface and an advantageous predeterminable adsorption/desorption ratio, with the active substances, for example inthe form of their solution (in a low-boiling solvent) and to remove the solvent. Such polymer granules can, in the form of micro-granules of bulk densities of preferably 300 g./litre to 600 g./litre,

' also be applied with the aid of atomisers. Atomising can be carried out over large areas of crop plant cultures by means of aircraft.

Of course pesticides, fertilisers, surface-active agents or substances for increasing thespecific gravity, such as BaSO can be added to the granules.

Granules are also obtainable by compacting the carrier material with the active substances and additives, and subsequent comminution.

The various use forms can, in the usual manner, be provided with additions of substances which improve the distribution, the adhesion, the rain resistance or the penetrating powergfatty acids, resin, glue, casein, or 'alginates may be mentioned as such substances.

In general, the agents contain between 0.01 and 95 percent by weight of active substance, preferably 0.1 to percent by weight. In certain special fields of use, for example in the case of applications by aircraft, technically pure active substance can also be employed and sprayed.

To broaden the spectrum of action, the active substances of Formula I can be combined with known insecticidal, acaricidal and/or nematocidal active substances, of which the following may for example be mentioned:

PHOSPHORIC ACID DERIVATIVES Bis-0,0-diethylphosphoric acid anhydride (TEPP) 0,0,0,0-tetrapropyldithiopyrophosphate Dimethyl(2,2,2-trichloro-1-hydroxyethyl)phosphonate (TRICHRORFON) 1,2-dibromho-2,2-dichlorethyldimethylphosphate (NALED) 2,2-dichlorovinyldimethylphosphate (DICHLORFOS) 2-methoxycarbamy1-1-methylvinyldimethylphosphate (MEVINPHOS) I Dimethyl- 1 -methyl-2- (methylcarb amoyl) vinylpho sphate cis (MONOCROTOPHOS) 3- dimethoxyphosphinyloxy) -N-methyl-N-methoxy-ciscrotonamide 3- dimethoxyphosphinyloxy) -N,N-dimethylciscrotonamide (DICROTOPHOS) 2-chloro-2-diethylcarbamoyl-l-methylvinyldimethylphosphate (PHOSPHAMIDON) 0,0-diethyl- O-2- (ethylthio) -ethylthiosposphate (DEMETON) 0,0-diethyl-S-2- ethylthio) -ethylthio phosphate S-ethylthioethyl-0,0-dimethyl-dithiophosphate (THIOMETON) 0,0-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE) 0,0-diethyl-S-2 ethylthio ethyl] dithiophosphate (D'ISULFOTON) 0,0-dimethyl-S-2- ethylsulphinyl) ethylthiopho sphate (OXYDEMETHONMETHYL) 0,0-dimethyl-S- 1,2-dicarbethoxyethyl) dithiophosphate (MALATHION) (0,0,0,0-tetraethyl-S,S'-methylene-bis-[dithiophosphate] (ETHION) O-ethyl-S,S-dipropyldithiophosphate 0,0-dimethyl-S-(N-methyl-N-formylcarbamoylmethyl)- dithiophosphate (FORMOTION) 0,0-dimethyl-S- (N-methylcarbamoylmethyl) dithiophosphate (DIMETHAT) 0,0-dimethy1-S- (N-ethylcarbamoylmethyl) dithiophosphate (ETHOATMETHYL) 0,0-diethyl-S- (N-isopropylcarbamoylmethyl) -dithio phosphate (PROTHO'AT) S-N-( l-cyano-1-methylethyl) carbamoylmethyldiethylthiolphosphate (CYANTHOAT) S- (Z-acetamidoethyl) -0,0-dimethyldithiopho sphate Hexamethylphosphoric acid triamide (HEMPA) 0,0-dimethyl-O-p-nitrophenylthiophosphate (PARATHION-METHYL) 0,0-diethyl-0-p-nitrophenylthiophosphate (PARATHION) O-ethyl-O-p-nitrophenylthiophosphonate (EPN) O, O-dimethyl- O- (4-nitro-m-tolyl) thiophosphate (FENITROTHION) 0,0-dimethyl- 0-(2-chloro-4-nitrophenyl)thiophosphate (DICAPTHON) 0,0-dimethyl-O-p-cyanophenylthiophosphate CYANOX) O-ethyl-O-p-cyanophenylphenylthiophosphonate 0,0-diethyl-O-2,4-dichlorophenylthiophosphate (DICHROFENTHION) O-2,4-dichlorophenyl-O-methylisopropylamidothiophosphate 9. 6-methyl-2-oxo:1.,3-dithiolo ..[4,5.-b].-.quinoxa1ie [Quinomethionat] (I)-3 Z-furfuryl) -2-mcthyl-4-oxocyclopent-Z-enyl (I) cis+trans) chrysanthemum-monocarboxylate [Furethrinl Z-pivaloyl-indane-1,3-dione [Pindon] 2-fiuorethyl (4-bisphenyl) acetate Z-fluoro-N-methyl-N 1-naphthyl)-acetamid Pentachlorophenol and salts 2,2,2-trichloro-N(pentachlorophenyl)-acetimidoyl chloride N'-(4-chloro-2-rnethylphenyl)-N,N-dimethylformamidine (Chlorophenamidine) 4-chlorobenzyl-4-fiuorophenyl-sulphide (Fluorobenside) 5,6-dichloro-l-phenyloxycarbanyl-Z-trifiuoromethylbenzimidazole (Fenozaflor) Tn'cyclohexyl-tin hydroxide Z-thiocyanatoethyl-lauric acid ester fl-Butoxy-H-thiocyanatodie'thyl-ether Isobornyl-thiocyanatoacetate p-Chlorophenyl-p-chlorobenzenesulphonate (Ovex) 2,4-dichlorophenyl-benzenesulphonate p-Chlorophenyhbenzenesulphonate (Fenson) p-Chlorophenyl-2,4,S-trichlorophenylsulphone (Tetradifon) p-Chlorophenyl-2,4,S-trichlorophenylsulphide (Tetrasul) Methyl bromide p-Chlorophenyl-phenylsulphone p-Chlorobenzyl-p-chlorophenylsulphide (Chlorobenside) 4-chlorophenyl-2,4,S-trichlorophenylazosulphide 2(p-tert.-Butylphenoxy-1-methyl-2-chloroethyl-sulphite 2(p-tert.-Butylphenoxy) cyclohexyl-Z-propionyl-sulphite 4,4'-dichloro-N-methylbenzenesulphonanilide N-(Z-fluoro- 1, 1,2,2-tetrachloroethylthio)methane sulphonanilide Z-thio-1,3-dithiolo-(4,5,6)quinoxaline (Thioquinox) Chloromethyl-p-chlorophenylsulphone (lauseto (sic!) new) 1,3,6,8-tetranitrocarbazole and Prop-2-ynyl-(4-t-butylphenoxy)-cyclohexylsulphite (propargyl).

The action of the phosphoric acid esters of the Formula I according to the present invention, can be increased by synergistic agents. Suitable substances for this purpose are, for example, Sesamine, Sesamex, piperonyl cyclonene, piperonyl butoxide, piperonal bis [2-(2-butoxyethoxy)ethyl] acetate, sulphoxides, propyl isome, N- (2-ethylhexyl)-5norbornene 2,3 dicarboxamide, octachlorodipropyl-ether, 2 nitrophenylpropargyl-ether, 4- chlor-Z-nitrophenyl-propargyl-ether, and 2,4,5-trichlorophenyl-propargyl-ether.

The present invention also provides a process for the manufacture of the phosphoric acid esters of the Formula I, which comprises reacting a dihalogenacetic acid ester of the formula (Hal) CHCOOR in which Hal represents a chlorine atom or a bromine atom and R has the meaning specified above, with a trialkylphosphite of the formula in which R and K, have the meanings specified above and R represents an alkyl radical having from 1 to 4 carbon atoms. The reaction can be carried out in a solvent, for example, toluene, xylene, petrol ether or dioxane, depending upon the speed or sluggishness of the particular reaction.

This reaction is surprising, since it is expressly stated in the literature (F. W. Lichtenthaler, Chem. Rev. 61, 612[1961]), in elaboration of the Perkow reaction, that the reaction of triethylphosphite with dichloroacetic acid 10 ethyl ester. onlyv yields undefined end products together With C H Cl. Dichloroacetic acid esters, so it is said, are not suitable for the Perkow reaction.

The following examples illustrate the invention.

EXAMPLE 1 0,0-diethyl-1-(4-chlorophenoxy)-2-chlorovinyl-phosphate 0.11.0 .i-0-i'3-0Q01 (Active substance N0. 1)

47.6 g. of dichloroacetic acid 4-chlorophenyl ester were dissolved in ml. of toluene. 40 g. of triethylphosphite were added to this solution, after which the reaction mixture was warmed to C. and kept at this temperature for 16 hours.

The toluene was subsequently distilled oil and the crude product was purified by means of a molecular distillation apparatus.

Yield 35.3 g.; boiling point: 100 C./0.003-0.004 mm. Hg

Analysis for C H Cl O P: Calculated (percent): P, 9.1; CI, 20.8. Found (percent): P, 8.9; CI, 21.3.

The structure of the product was confirmed by means of infrared analysis. On addition of SO Cl in CH Cl C1 was added to the double bond. The resulting yellowish trichloroehtyl phosphate shows the following analytical figures for C H Cl O P:

Calculated (percent): P, 7.52; Cl, 34.42. Found (percent): P, 7.7; C], 34.9.

The following phosphoric acid esters can be obtained in a similar manner:

Active substance Boiling point/ No. R =Rz Hal R mm. Hg

2 C2H5 Cl 100 C./0.001.

3 CH C1 124 C./0.005.

4 CH3 o1 c./0.001.

5 CH o1 130 o./0.001.

7- CH C1 135 C./0.O0q.

8 CzHs Cl 135 C./O.OO1.

9 C2115 Cl 135 C./O.O[)1.1

Active substance Boiling point] N R1=Rz Hal R3 mm. Hg

46 CzH Cl (3H 136 (IL/0.001..

47 C2H5 Cl 130 C./0.001.

48 CzH Cl 135 C./0.005.

49.-'.'.'.'.. 02H; C1 135 C./O.005.

50 02H 01 CaCI5 180 C./0.08.

51...... CH; Cl 125 C'./0.O01.

52...--- C2H5 Cl 1'31 145 C./0.005.

I O CH;

53 C2H5 Cl ()1 140 C./0.001.

I C1 C1 54 C2H4 Cl 140 C./0.005.

COCH

56 C2H5 01 Q 140 o./0.005.

57 C211 C1 0 140 C./0.C05.

I C 0-0 H;

1 Molecular distillation.

as well as compounds 58 O HC-Br Boiling pointmns l! I 142-146 0. (C2H5O)2POC-O CI 59- O HC-Br Boiling point m H I] 145-149 0. (C2H O)2POCO Cl 60 0 HCBr Cannot be II II distilled. (C2H50)zPO-CO- N02 61 0 110-131 Boiling point H H 0.02 13$"C. (C2H5O)2POC-O C1 62 O HC-Br Boiling point i] H 0.001 128 C (C2H O)zPO-CO Cl Boiling point 63 0 HC-Br (I) HC-Br Boiling point Boiling point I 0. 2 151 0.

C1 CH3 3 Boiling point CH HCB! I 0.0 148-195 C.

0 wnnonii-o-t'LoQm Boiling point 0 01 129 C.

Boiling point 1 Molecular distillation.

EXAMPLE 2 (a) Dusting agents Equal parts of an active substance according to the invention and of precipitated silica are finely ground. Dusting agents preferably containing 16% of active substance can be manufactured therefrom by mixing with kaolin or talc.

(a) Spraying powders In order to manufacture a spraying powder, the following components are for example mixed and finely ground:

(c) Emulsion concentrate Easily soluble active substances can also be formulated as an emulsion concentrate according to the following instruction:

20 parts 70 parts of xylene and 10 parts ofa mixture of the reaction product of an alkyl phenol with ethylene oxide and calcium dodecylbenzene sulphonate are mixed. On dilution with water to the desired concentration, a sprayable emulsion is produced.

(d) Granules (a) 7.5 g. of one of the active substances of Formula I are dissolved in m1. of acetone and the acetone solution thus obtained is added to 92 g. of granular attapulgite (mesh size: 24/48 meshes/ inch). The whole is well mixed and the solvent is stripped oil? in a rotary evaporator. Granules containing 7.5% 'of active substance are obtained.

of pulverulent, porous polyacrylonitrile are pressed on a roll mill and subsequently crushed to the desired particle size.

EXAMPLE 3 Contact action on Musca domestica (L.) and Ceratitis capitata 1 half of each of a series of Petri dishes was treated with 1 ml. of an acetone solution of substance No. 1 con taining 1000, 100, 10, 5, 2.5 and 1.25 ppm. of the active substance. After evaporation of the solvent, 10 supercooled house flies were'introduced into each of the preparedPetri dishes, and the lid halves were placed on top. After increasing time intervals, the destruction was checked at the various concentrations. The following destruction in percent was achieved after 2 hours:

ACTIVE SUBSTANCE No.1

Musca Cerat-itia domestica capitata Concentration (ppm):

EXAMPLE 4 Action against Spodoptera littoralis larvae 5 larvae at a time, in the L-2 stage, are placed on a leaf of Malva silvestris which originates from a plant dipped into an aqueous solution of an active substance, 1

v and which had subsequently been introduced into a covered Petri dish. The atmospheric moisture in the dish is maintained with a moistened pad of cottonwool. In this contact test and ingestion test the action was examined after 1 day and after 2 days. If complete destruction has already occurred after 1 day for a particular concentra: tion, a fresh leaf of the same plant is infested with a new population. In this way a possible ageing of the active substance coating is also taken into account in the assessment.

For active substance No. 25, the follOWing destruction percentages were found:

1 day 2 days Concentration (p.p.m.):

EXAMPLE 5 (a) The test with Epilachna varivestis, the Mexican bean bug, was carried out as follows: 4-5 seedlings of Phaseolus vulgaris in the primary leaf stage', grown in a flower pot, were dipped intoemulsions of the experimental preparations and subsequently allowed to dry. The

experimental animals,- L-4 stage of the bettle, were in- .troduced into a cellophane bag which was subsequently fixed over the treated plant by means of a rubber band. After 5 days, the action of the treatment Was determined 16 by counting the live and dead animals and by calculating thepercentage destruction. For active substance No. 43 the following percentage of destructionwere found:

Concentration [p.p.m.]: 5 days 800 -a 100 400 100 200 100 (b) The test with Orgyia gonostigma in the L-3 stage was carried out analogously with young mallows (Malva silvestris) as the host plant. 5 larvae were used for each experiment. The results were assessed after 2 and 5 days. If complete destruction had already occurred after 2 days, the plant was again infested. In this way a possible ageing of the active substance coating is also taken into account in the assessment.

For active substance No. 21 the following percentages of destruction were achieved:

2 days 5 days Concentration (p.p.m.):

EXAMPLE 6 Action against Chilo suppressalis (larvae) Active substances Nos. 1 and 2 were tested for their ingestion action against L-2 larvae. For this test, the larvae were placed on the root structure of rice seedlings which had previously been treated by dipping in an emulsion of the active substance.

The evaluation took place after 5 days.

Mortality in percent for active substance No. 1 and No. 2

Concentration of the active substance in the emulsion, p.p.m.:

EXAMPLE 7 Action against Aphis fabae Young Vicia faba plants approx. 6 cm. high were infested with parts of plants attacked by A phis fabae. After 5 days the starting conditions for the active substance test were present, as a result of the further growth of the plants and appropriately strong multiplication of the aphids. The attacked plants were sprayed with theernulsions of active substance No. 25 from all sides (contact action), or only from above in the direction of the shoot axis (penetration action). In the latter case, the experimental animals sitting on the. undersides of the leaves were not struck by the spray jet. If 100% destruction had already occurred after 2 days, the plants were re-infested.

Active substance No. 25 achieved the following percentages of destruction after 2 and 5 days:

Contact action Penetration, 2 days 5 days 2 days Concentration (p.p.m.):

EXAMPLE 8 Action against spider mites Busch bean plants (Phaseolus vulgaris) in the 2-leaf stage were infested with spider mites, 12 hours before the treatment with the active substance, by placing attacked pieces of leaf from a culture on them, so that after the end of this time a population in all stages of development was present on the plant. The plants were then sprayed with the emulsified active substance by means of a chromatography atomiser, until a uniform deposit of droplets was produced on the surface of the leaf. The results were assessed after 2 and 7 days; the parts of the plant were inspected under a stereo-microscope in order to calculate the percentages of destruction. The action on eggs was not yet detectable after 2 days with this experimental arrangement, because the embryo development takes 4 days under the particular conditions. If after 2 days there was 100% destruction of larvae and adults, the plant was re-infested.

The percentages of destruction of the normally sensitive variety Tetranychus urticae Koch and of the phosphoric acid ester-tolerant variety Tetranychus telarz'us L. are given in the table below.

ACTIVE SUBSTANCE NO. 1

(a) Action against Tetr. umcae Destruction Destruction after 2 days after 7 days Concentration (p.p.m.) Larvae Adults Eggs Larvae Adults (1)) Action against Tetr. telarius ACTIVE SUBSTANCE NO.

(a) Action against Tetr. urticae Destruction Destruction after 2 days after 7 days Concentration (p.p.m.) Larvae Adults Eggs Larvae Adults (b) Action against Tetr. Marina EXAMPLE 9 Action against ectoparasites and vectors Ticks (A) Rhipicephalus bursa (adults). The experimental animals were briefly treated with aqueous solutions of a dilution series of the active substance. Assessment after 2 weeks.

(b) Rhipicephalus bursa (larvae). Method as under (A).

Assessment after 3 days. (C) Boophilus microplus (larvae). Method as under (B) Assessment after 3 days.

Vectors (D) Lucilia sericata (larvae). Chopped horsemeat. mixed with dilution concentrations of an active substance, were administered as food to the larvae of the blow-fly. Assessment after 24 hours.

(E) Ades aegvptzl (larvae). The larvae of the yellow fever mosquito were kept in a very dilute aqueous solution of active substance. Assessment after 24 hours.

MINIMUM CONCENTRATIOTNIgIgOR COMPLETE DESTRUC- Parts per million Active substance No. A B C D E EXAMPLE 10 Action against storage pests when using a 5% strength dust formulation based on talc.

hours exposure time.

EXAMPLE 11 Fungicidal action (1) Rice plants were grown in a greenhouse and sprayed one, prophylactically, with an aqueous spraying liquor containing 0.1% of the active substance No. 21. Two days thereafter, the plants treated in this way were infected with conidia of Piricularia oryzae Bri. and Cav. After 7 days incubation in a humidity chamber, the plants treated with the experimental preparation showed a fungal attack of about 10%, Whilst the untreated control plants were 100% attacked.

(2) Small agar plates on which Rhizoctonz'a solani Kt'ihn had grown were covered, in petri dishes, with nonsterile soil. An aqueous liquor containing active substance No. 38 which was to be tested, was uniformly distributed over the surface of these layers of soil. After an incubation time of 48 hours at 24 C. the growth of the test fungus was examined and assessed. Herein, a test concentration of 100 ppm. of active substance showed complete inhibition of fungal growth.

in which Hal represents a chlorine atom or a bromine atom, R and R which may be the same or different each represents an alkyl radical having from 1 to 4 carbon atoms and R represents an aryl radical, especially a phenyl or naphthyl radical, which may be substituted by an alkyl, alkoxy or alkylthio radical each having from 1 to 4 carbon atoms, NO CF -CN, or a COO- alkyl or Calkyl radical, the alkyl moieties of which each have from 1 to 4 carbon atoms.

2. A compound according to claim 1, in which Hal represents a chlorine atom or a bromine atom, R and R each represent a methylor ethyl radical and R represents a phenyl group which may be substituted by from 1 to 5 of the following substituents:

halogen, methyl, ethyl, methoxy, ethoxy, methylmercapto, --NO CF CN, carbethoxy, carbomethoxy, acetyl or propionyl.

3. A compound according to claim ;1, in which Hal represents a chlorine atom and R represents a phenyl grup substituted by from 1 to 5 of the substituents:

chlorine, bromine, iodine, CN, NO or -CF and which may also contain a methyl or ethyl group.

4. The compound of the formula I I according to claim 1.

5. The compound of the formula HC-Ol according to claim 1.

6. The compound of the formula according to claim 1.

7. The compound of the formula BIG-C1 according to claim 1.

8. The compound of the formula according to claim 1. p 9. The compound of the formula according to claim 1.

10. The compound of the formula Ito-01 according to claim 1. v

. 20 11. The compound of the formula according to claim 1.

12. The compound of the formula CH3 0 BIC-01 i according to claim 1.

14. The compound of the formula according to claim 1.

15. The compound of the formula (onnoni-b-ii-o-Qm according to claim 1.

16. The compound of the formula according to claim 1. r p

17. The compound of the formula according to claim 1. V

18. The compound of the formula according to claim 1.

UNITED STATES PATENTS References Cited 1 2,861,914 11/1958 Sallmann 260-951 X LEWIS GOTTS, Primary Examiner A. H. SUTIO, Assistant Examiner US. Cl. X.R. 

